Polyamines

Newly Discovered Hormones

• Polyamines (Putrescine, Spermidine, Sperrmine, Cadaverine )
• Brassinosteroids
• Salicylic acid (cut flowers and leafy vegetables)
• Jasmonates (inhibitors)
• Systemin
• Alpha Tocopherols (antioxidants)
• Fusicoccin (from Fusariutn amygdali)
• Triacontanol (growth promoter extracted from alfalfa)
• Turgorins
• Batasins (causes dormancy in bulbils. Extracted from yam.)
 Polyamines
• Definition
– Those hormones or compounds which
possess two or more then two amino group.

– These are the polyvalent cation compounds

that contains two or more amino groups.
 Polyamines
• The diamine putrescine, the triamine spermidine and the tetramine
spermine are ubiquitous in plant cells (Smith et al, 1979; Bagni and
Pistocchi, 1992).
• They occur as free cations and as conjugates with phenolic acids
and macromolecules (Galston and Sawnhey, 1990).
• Their levels increase greatly in response to environmental stresses,
most notably under conditions of potassium deficiency, water
deficits, salinity stress, anaerobiosis and acid stress (Flores et al,
1989).
• Because polyamines are synthesized by amino acid decarboxylation
reactions which consume H+, polyamine accumulation may function
as part of a homeostatic mechanism to keep intracellular pH at a
constant value (Flores et al, 1985).
• Polyamines may also play a role in the regulation of DNA replication
and cell division, and are implicated in the control of senescence and
morphogenesis (Evans and Malmberg, 1989; Galston and Sawnhey,
1990).
• It has been proposed that polyamines could be part of an intrinsic
signaling network of the extracellular matrix (Messiaen et al, 1997).
Polyamines also serve as precursors of several classes of alkaloids
(Smith et al, 1979; Flores et al, 1989; Hashimoto and Yamada, 1994)
which may play important roles in plant defense against herbivores.
 Polyamines
• Types
• Among the most abundant and
physiologically active polyamines are

• Putrescine
• Spermidine
• Spermine
• Cadaverine
 Putrescine
• Putrescine (sometimes spelled putrescin or
putrescene) is an organic chemical compound NH2(C
H2)4NH2 (1,4-diaminobutane or butanediamine) formed
by and having the smell of rotting flesh.
• It is related to cadaverine; both are produced by the
breakdown of amino acids in living and dead organisms.
Putrescine and cadaverine were first described by the
Berlin physician Ludwig Brieger in 1885.
• Putrescine is synthesized in small quantities by healthy
living cells by the action of ornithine decarboxylase. The
polyamines, of which putrescine is one of the simplest,
appear to be growth factors necessary for cell division.
 Putrescine

                                             

Chemical name 1,4-Diaminobutane

Other names Tetramethylenediamine

Butane-1,4-diamine

Chemical formula C4H12N2

Molecular mass 88.15 g/mol

Density 0.877 g/cm³

Melting point 27 °C

Boiling point 158-160 °C

Putrescine Synthesis
 Arginine decarboxylase (ADC)
• Arginine decarboxylase (ADC) (a
chloroplast localized enzyme (Borrell et al,
1995)) is induced by a variety of stresses
(most notably potassium deficiency;
Watson and Malmberg, 1996) and is
thought to be the enzyme primarily
responsible for environmental stress-
induced putrescine accumulation (Galston
and Sawnhey, 1990):
 Physiological Roles of Putrescine
• Arginine decarboxylase of oats is clipped from a precursor into two
polypeptides found in the soluble enzyme (Malmberg et al, 1992). The
two polypetides are linked by disulfide bonds to form the active
enzyme (Watson and Malmberg, 1996).
• The oat (Bell and Malmberg, 1990), tomato (Rastogi et al, 1993), and
Arabidopsis arginine decarboxylase (Watson and Malmberg, 1996)
genes have been cloned.
• In Arabidopsis, arginine decarboxylase enzyme levels do not
correspond to ADC protein amounts, suggesting post-translational
modification of the enzyme in response to potassium deficiency
(Watson and Malmberg, 1996). In osmotically stressed oat leaves
spermine inhibits post-translational processing of the ADC precursor,
with subsequent decreases in mature ADC (Borrell et al, 1996).
• Loss of regeneration capacity of rice in long term culture is associated
with massive accumulation of putrescine due to an increase in
arginine decarboxylase activity. Difluoromethylarginine, an inhibitor or
arginine decarboxylase, restored regeneration capacity to long-term
cultures (Bajaj and Rajam, 1996). Spermidine treatment also caused
a reduction in putrescine content and arginine decarboxylase activity
and restoration of plant regeneration ability (Bajaj and Rajam, 1996).
In contrast, putrescine promotes and difluoromethylarginine inhibits
somatic embryogenesis in eggplant (Yadav and Rajam, 1998).
• The alternative, more direct pathway of synthesis of putresine via
ornithine decarboxylation catalyzed by cytosolic ornithine
decarboxylase (ODC) [EC 4.1.1.17] is proposed to be of little
importance in stress-induced putrescine accumulation, but may be
critical in regulation of developmental processes (Galston and
Sawhney, 1990; Walden et al, 1997). Increased putrescine
biosynthesis catalyzed by ornithine decarboxylase promotes somatic
embryogenesis in carrots (Bastola and Minocha, 1995). Increased
production of putrescine in carrot cells expressing mouse ODC is
accompanied by increased putrescine catabolism (Andersen et al,
1998).
• Levels of putrescine are higher in a drought tolerant wheat cultivar in
comparison to a drought suceptible wheat cultivar. These wheat
cultivars also differ for oxidant stress resistance as assayed by
resistance to paraquat (Ye et al, 1997). Constitutively elevated levels
of Arg decarboxylase and Orn decarboxylase are correlated with
paraquat resistance in Conzya bonariensis (Ye et al, 1997). Arg
decarboxylase and Orn decarboxylase are differentially regulated in
Conzya bonariensis, with only the former detectable in 2 week-old
plants. Orn decarboxylase becomes more abundant than Arg
decarboxylase in 10 week-old plants (Ye et al, 1997). Exogenously
supplied putrescine prevents oxidative damage in paraquat-resistant
C. bonariensis (Ye et al, 1997). In part this may be due to inhibition
of paraquat uptake by putrescine (Hart et al, 1993). Ye et al (1997)
suggest that putrescine and other polyamines could function directly
or indirectly as free radical scavengers.
 Cadaverine
• Cadaverine is a foul-smelling molecule produced by
protein hydrolysis during putrefaction of animal tissue.
Cadaverine is a toxic diamine with the formula
NH2(CH2)5NH2, which is similar to putrescine.
Cadaverine is also known by the names 1,5-
pentanediamine and pentamethylenediamine
Cadaverine is the decarboxylation product of the
amino acid lysine.
• However, this diamine is not purely associated with
putrefaction. It is also produced in small quantities by
living beings. It is partially responsible for the distinctive
smell of urine and semen
 Cadaverine

                                                            

Chemical name 1,5-diaminopentane

Other names pentamethylenediamine

pentane-1,5-diamine

Chemical formula C5H14N2

Molecular mass 102.18 g/mol

Density 0.870 g/cm³

Melting point 9 °C

Boiling point 178-180 °C

 Biosynthesis of Putrescine &
Cadaverine

The diamine cadaverine is derived from the amino acid lysine by decarboxylation. Its
synthesis is catalyzed by lysine decarboxylase [EC 4.1.1.18]. Cadaverine may play an
important role in root development (Gamarnik and Frydman, 1991).
 Spermine
• Spermine is a polyamine involved in cellular metabolism
found in all eukaryotic cells. Formed from spermidine, it is
found in a wide variety of organisms and tissues and is
an essential growth factor in some bacteria. It is found as
a polycation at physiological pH. Spermine is associated
with nucleic acids and is thought to stabilize helical
structure, particularly in viruses.
• Crystals of spermine phosphate were first described in
1678, in human semen, by Anton van Leeuwenhoek. The
name spermin [sic] was first used by the German
chemists Ladenburg and Abel in 1888[2], and the correct
structure of spermine was not finally established until
1926, simultaneously in England (by Dudley, Rosenheim,
and Starling) and Germany (by Wrede. et al).
 Spermine

                                                     

Systematic name N,N'-bis(3-aminopropyl)butane-1,4-

diamine
Other names gerontine, musculamine and neuridine

Chemical formul C10H26N4

a

Molecular mass 202.34 g/mol

Density x.xxx g/cm3

Melting point 29°C

Boiling point xx.x °C

 Spermidine
• Spermidine is a polyamine involved in
cellular metabolism that can be used to stimulate
the enzyme, T7 rna polymerase, a type of
RNA polymerase.
• Inhibits neuronal nitric oxide synthase (nNOS).
• Binds and precipitates DNA.
• May be used for purification of DNA binding
proteins.
• Stimulates T4 polynucleotide kinase activity.
 Spermidine

                                              

Systematic name N-(3-aminopropyl)butane-1,4-diamine

N-(3-aminopropyl)-1,4-diaminobutane
Chemical formula C7H19N3
Molecular mass 145.25 g/mol
Properties
Density 0.925 g/mL at 25 °C
Melting point xx.x °C
Boiling point xx.x °C
Refractive index n20/D 1.479(lit.)
Foreign activity DNase, RNase, and protease, none detected
Storage temp. 2-8°C
 Biosynthesis of Spermidine & Spermine

Spermidine, and spermine are synthesized from L-arginine and L-ornithine. Synthesis
of spermidine and spermine requires an aminopropyl group derived from SAM, and
there may be competition between the ethylene and polyamine biosynthesis pathways
when concentrations of SAM are limited. The primary (terminal) amines of polyamines
are oxidized by diamine oxidases, the secondary amines by polyamine oxidases.
 Spermidine and spermine synthesis

The condensation of decarboxylated SAM and putrescine is catalyzed by spermidine

synthase (putrescine aminopropyltransferase) [EC 2.5.1.16]. Further condensation of
spermidine with decarboxylated SAM, catalyzed by spermine synthase [EC 2.5.1.22],
produces the tetramine, spermine (Flores et al, 1989).
Metabolism of Polyamines
 Metabolism of Polyamines
• In addition to serving as a precursor of spermidine and
spermine, putrescine has three other metabolic fates;
conjugation with hydroxycinnamic acids, metabolism to
gamma-aminobutyrate (GABA), and utilization in alkaloid
biosynthesis.
• (see also discussion of GABA metabolism under
Aminotransferase reactions)
• GABA can be derived from putrescine (via gamma-
aminobutyraldehyde) through the reactions catalyzed by
diamine oxidase [EC 1.4.3.6] and gamma-
aminobutyraldehyde dehydrogenase (Flores et al, 1989).
As noted in the discussion of Quaternary ammonium and
tertiary sulfonium compounds, the latter enzyme may be
the same as BADH involved in glycinebetaine synthesis
(Trossat et al, 1997).
• Putrescine serves as precursor of the nicotine and
tropane alkaloids (Smith et al, 1979; Flores et al, 1989;
Hashimoto and Yamada, 1994), which may play
important roles in plant defense against herbivores.
 Mode of action of Polyamines
• Bonding
– In polyamine, amino group contains +ve charge on
NH+3 Which helps to bind with –vely charged
phosphate group of DNA and RNA. As a result of this
combination, they often increase transcription of DNA
and translation of RNA. They enhance or stimulate
protein synthesis.
Cell cycle regulation
– Polyamines cause phosphorylation of proteins, they
are involved in the regulation of cell cycle by
controlling the phosphorylation of proteins that take
part in cell cycle.
Hydroxycinnamic acid conjugates of polyamines
Hydroxycinnamic acid conjugates of polyamines

• Hydroxycinnamic amide (HCA) conjugates of

polyamines accumulate markedly in the floral
apex during flower development, and are
implicated in the development of competence to
flower; certain mutants of tobacco which are
deficient in HCAs are unable to flower, and male
sterile mutants of maize lack HCA accumulation
in anthers (Flores et al, 1989). A novel
polyamine conjugate, N4-hexanoylspermidine,
has been identified in senescing pea ovaries
and petals (Perez-Amador et al, 1996).
 Physiological Functions of Polyamines
• Membrane Stabilization – Stabilize Membrane Structure and Function e.g.
Thylakoid
• DNA Stabilization – Interaction with Nucleic acid Spm-DNA complexes
stabilize DNAs against thermal denaturation. Spd also has same effects.
• Enzyme Activity – Stimulate enzyme activity e.g. Kinases in animals and and
F 1,6 bisphosphate in plant
• Cell Division – Enhance Cell Division but polyamines are not involved in Cell
Elongation
• Buffering of Cellular pH – The reversible protonation of multiple amino
groups of PAs, serves as buffer in the cells
• Role in Flowering – Floral axis synthesize large quantities of conjugate PAs
de novo
• Development of Ovary and Ovule – The development of the ovary and
ovules and ovules during maturation seems highly sensitive to PAs.
• Embryogenesis – Increases embryogenesis
• Senescence – At the time of senescence, there is low amount of Pas.
• Abiotic Stress Tolerance – Play significant role in abiotic stresses tolerance
like chilling, drought and salinity.
• Auxin Correlation -Since auxin application increases PAs in plants, it is
proposed that auxins act through PAs to promote growth
• Tuber formation,
• Root initiation
• Fruit ripening